Alkenyl-3, 4, 5, 6-tetrahydropyridine compounds



United States Patent No Drawing. Filed Oct. 11, 1965, Ser. No.

6 Claims. (Cl. 260-296) ABSTRACT OF THE DISCLOSURE Alkeny1-3,4,5,6-tetrahydropyridine compounds of the formula n CHzCHgCHzNHz N R wherein R is hydrogen, a hydrocarbon substituent, or aminopropyl, R is a hydrocarbon substituent; and at least one of R and R is alkenyl or cycloalkenyl. The compounds are useful as fungicides and pesticides.

This invention relates to ethylenically unsaturated amines.

More particularly this invention relates to 3,4,5,6-tetrahydropyridines of the formulapenyl, isopropenyl, butenyl, isobutenyl, allyl, crotyl; and

cyclobutenyl, cyclopencycloheptadecenyl; mixed aliphatic-arocycloalkenyl, e.g., cyclopropenyl, tenyl, cyclohexenyl, cycloheptenyl, and the like. Typical aromatic and matic hydrocarbon substituents are aryl, e.g., 'phenyl, naphthyl, and anthracyl; aralkyl, e.g., benzyl; alkaryl, e.g., tolyl (ortho, meta, para); alkaralkyl, e.g., xylyl (ortho, meta, para), and the like. Preferred hydrocarbon substituents are those containing up to and including 18 carbon plated, including the various isomers, drocarbon-substituted homologs, thereof. Moreover, it will be seen from Formula I that one or both of R and R must be alkenyl or cycloalkenyl, including structures wherein one of R and R is alkenyl and the other is cycloalkenyl.

The terthydropyridines defined by Formula I above are prepared by hydrogenatmg known dior tricyanotautomers, and hypreparing novel piperidine compounds by hydrogenation in which the hydrogenation may be interrupted before complete reaction and a tetrahydropyridine intermediate isolated. Thereafter, in a second step, the tetrahydropyridine compound may be hydrogenated further to form the piperidine. The instant tetrahydropyridines therefore are prepared by incomplete hydrogenation of a corresponding dior tricyanoethylated ketone having as a substituent at least one of alkenyl and cycloalkenyl in accordance with the equation:

R! [I H, CHzCHgCHgNHz RCC(CH2CH2CN)2 I eat. N

wherein R and R are as defined above.

The compounds of this invention possess dual functionality in that they contain both an amine group and ethylenic unsaturation. Hence these compounds undergo reactions which are typical of amines and ethylenically unsaturated compounds and are therefore useful in preparing a wide range of derivatives based on these reactions. For example, alkylene oxides and isocyanates react with the amine group to form amino-alcohol compounds and urea compositions, respectively. By virtue of the ethylenic unsaturation the amino-alcohol or ureas can then be copolymerized with such well-known monomers as ethylene, propylene, styrene, vinyl chloride, vinylidene acid, methacrylic acid,

r butadiene-1,3, isoprene, allyl compounds such as diallyl mixtures of two or more of the foregoing, and the like. It will also be apparent that the instant tetrahydropyridines are useful as co-reactants with the foregoing monomers to provide copolymers containing free amino groups for subsequent reaction with alcohols or isocyanates. The completed polymers, co-polymers, or crosslinked materials incorporating the instant tetrahydropyridine compounds are thermoplastic resins useful for the manufacture of molded products and films having known and virtuall unlimited utility in industrial and consumer products.

The instant tetrahydropyridines are also useful as fungicides and pesticides particularly for the protection of plants.

EXAMPLE I To a rocking autoclave is charged 30.6 grams (0.15 moles) of 4-acetyl-4-isopropenylheptanedinitrile, 2.0

C. and 700-1400 p.s.i.g. hydrogen pressure and filtered. The react on product is then purified by vacuum distillatron to give 22.2 grams yield) of 3-(3-aminoagogszr Identification of this produce was made by infrared spectrum and elementary analyses: Calcd'for C H N z C, 74.17%; H, 11.41%; N, 14.42%. Found: C, 74.60,

EXAMPLES 29 In essentially the same manner as described in Example 1 1, the following tetrahydropyridines are prepared by catalytic hydrogenation of the corresponding ketones:

Ketone Product CH 0 l =CH2 2.- 051.15% C CHgQHzCN) 2 CH2CH2CH2NH2 =CHZ (3H N Cam 4-benzoyl-4-isopropenylhcptanedinitrile 3-(3-aminopropyl)-3- isopropenyl-2-phenyl-3,4,5,t

tetrahydropyridine CH2CH2CHQNHZ I 3. CHFCHCUJHzCHzCN): CsHs N CH=CH2 4-acrylyl-4-phenylheptanedinitrile 3-(3-aminopropyl)-3-phenyl- 2-vinyl-3,4,5,fi-tetrahydropyridine C H: 0 Ha ll 4. CoHsCHzC C (CHZCH CN) z H=CH3 4-erotonyl-4-methylheptanedinitrile 3-(S-aminopropyl)-2-metliyl-3 propeny1-3,4,5,6-tetrahydropyridine pyridine -cinuamoyli-cyclopcntylheptanddif 3-(3-aminopropyU-3 mtrile eyelopentyl-Z-styryl-3,4,5,6- tetrahydropyridine;

H CH2 0 C=CH2 9. /C- -C(CHzCHzNH2)z I CHzCH2CH2NHz H30 IZCHZ o CH 2 H3O \N// i 4-is0propeuyl-4-methacry\ylheptanedi- '3-(3-aminopr0pyl) -2,3-dir, nitrile isopropenyl-3,4,5,6-tetrahydropyridine What is claimed is: w 1. A compoundof-the formula RI CH QH CHzNHa wherein R is selected from the group consisting of hydrogen, lower alkyl, cyclohexyl,.; isopropenyl, vinyl, styryl, phenyl and benzyl. R is selected from the group consisting of lower alkyl, cyclohexyl, iS0pr0penyl, vinyl, styryl, phenyl and benzyl. I 2. 3 (3 aminopropyl) 3 isopropenyl 2 methyl- 3,4,5,6 tetrahydropyridine.

3. 3 (3 aminopropyl) 3 isopropenyl 2 phenyl- 3,4,5,6 -'tetrahydropyridine. z 4. 3 (3 aminopropyl) 3 phenyl 2 vinyl 3, 4,5,6 tetrahydropyridine. I

5. 3 (3 aminopropyl) 2 cyclohexyl 3 isopropenyl 3',4,5,6 tetrahydropyridine.

6. 3 (3 aminopropyl) 2 methyl 3 propenyl: 3,4,5,6 tetrahydropyridine.

References Cited HENRY R. JILES, Primary Examiner. L. Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,409,627 November 5 1968 Richard Parke Welcher et a1.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4 line 41, after "benzyl" the period should be a comma; line 43, "benzyl. should read benzyl; and at least one of R and R is alkenyl.

Signed and sealed this 17th day of March 1970.

(SEAL) Attest:

Edward M. Fletcher, Jr. Attesting Officer Commissioner of Patents 

